Nitriding of niobium steel and product made thereby

ABSTRACT

A nitrided steel product or thin cast steel strip comprising, by weight, less than 0.25% carbon, between 0.20 and 2.0% manganese, between 0.05 and 0.50% silicon, less than 0.01% aluminum, niobium between 0.01 and about 0.20%, and between 0.01 and 0.075% nitrogen, and having a majority of the microstructure comprised of bainite and acicular ferrite, having more than 70% niobium in solid solution prior to nitriding and having after nitriding for one hour yield strength between 600 MPa and 800 MPa and tensile strength between 650 MPa and 900 MPa and no more than a 2% decrease in total elongation from the steel product prior to nitriding.

CROSS-REFERENCE TO RELATED APPLICATIONS

This patent application is a continuation-in-part of and claims priority to and the benefit of U.S. patent application Ser. No. 13/030,170, filed on Feb. 18, 2011, now U.S. Patent Application Publication No. 2011/0277886, which claims priority to and the benefit of U.S. Provisional Patent Application Ser. No. 61/306,471, filed on Feb. 20, 2010, the disclosures of which are hereby incorporated by reference in their entirety.

BACKGROUND AND SUMMARY

This invention relates to making of high strength thin cast strip, and the method for making such cast strip by a twin roll caster.

In a twin roll caster, molten metal is introduced between a pair of counter-rotated, internally cooled casting rolls so that metal shells solidify on the moving roll surfaces, and are brought together at the nip between them to produce a solidified strip product, delivered downwardly from the nip between the casting rolls. The term “nip” is used herein to refer to the general region at which the casting rolls are closest together. The molten metal is poured from a ladle through a metal delivery system comprised of a tundish and a core nozzle located above the nip to form a casting pool of molten metal, supported on the casting surfaces of the rolls above the nip and extending along the length of the nip. This casting pool is usually confined between refractory side plates or dams held in sliding engagement with the end surfaces of the rolls so as to dam the two ends of the casting pool against outflow.

In the past, high-strength low-carbon thin strip with yield strengths of 60 ksi (413 MPa) and higher, in strip thicknesses less than 3.0 mm, have been made by recovery annealing of cold rolled strip. Cold rolling was required to produce the desired thickness. The cold roll strip was then recovery annealed to improve the ductility without significantly reducing the strength. However, the final ductility of the resulting strip still was relatively low and the strip would not achieve total elongation levels over 6%, which is required for structural steels by building codes for structural components. Such recovery annealed cold rolled, low-carbon steel was generally suitable only for simple forming operations, e.g., roll forming and bending. To produce this steel strip with higher ductility was not technically feasible in these final strip thicknesses using the cold rolled and recovery annealed manufacturing route.

In the past, high strength, low carbon steel strip have also been made by microalloying with elements such as niobium, vanadium, titanium or molybdenum, and hot rolling to achieve the desired thickness and strength level. Such microalloying required expensive and high levels of niobium, vanadium, titanium or molybdenum and resulted in formation of a bainite-ferrite microstructure typically with 10 to 20% bainite. See U.S. Pat. No. 6,488,790. Alternately, the microstructure could be ferrite with 10-20% pearlite. Hot rolling the strip resulted in the partial precipitation of these alloying elements. As a result, relatively high alloying levels of the Nb, V, Ti or Mo elements were required to provide enough precipitation hardening of the predominately ferritic transformed microstructure to achieve the required strength levels. These high microalloying levels significantly raised the hot rolling loads needed and restricted the thickness range of the hot rolled strip that could be economically and practically produced. Such alloyed high strength strip could be directly used for galvanizing after pickling for the thicker end of the product range greater than 3 mm in thickness.

However, making of high strength, low carbon steel strip less than 3 mm in thickness with microalloying additions of Nb, V, Ti or Mo to the base steel chemistry was very difficult, particularly for wide strip due to the high rolling loads, and not always commercially feasible. For lower thicknesses of strip, cold rolling was required; however, the high strength of the hot rolled strip made such cold rolling difficult because of the high cold roll loadings required to reduce the thickness of the strip. These high alloying levels also considerably raised the recrystallization annealing temperature needed, requiring expensive to build and operate annealing lines capable of achieving the high annealing temperature needed for full recrystallization annealing of the cold rolled strip.

In short, the application of previously known microalloying practices with Ni, V, Ti or Mo elements to produce high strength thin strip could not be commercially produced economically because of the high alloying costs, difficulties with high rolling loads in hot rolling and cold rolling, and the high recrystallization annealing temperatures required.

Twin roll casting has enabled development of both plain C steel and Nb-microalloyed steel thin cast strip. An as-received 0.084 wt % Nb-microalloyed steel has been able to produced having a yield strength of 475 MPa with 14% total elongation. Previous studies have shown that with developed compositions, Nb atoms stay in the matrix as a solid solution with relatively fast cooling rate which can be achieved with twin roll casting. C and N contents in these steel compositions are quite low (0.031 and 0.007 wt % respectively) and the thickness of the as-hot-rolled steel sheets can be around 1.1 mm, so rapid diffusion of N into the steel composition is possible. We have found that the Nb-microalloyed steel properties can be further improved by nitriding.

Presently disclosed is a nitrided steel product comprised, by weight, less than 0.25% carbon, between 0.20 and 2.0% manganese, between 0.05 and 0.50% silicon, less than 0.01% aluminum, niobium between 0.01 and about 0.20%, and between 0.01 and 0.075% nitrogen. The steel product has a majority of the microstructure comprised of bainite and acicular ferrite, with more than 70% niobium in solid solution prior to nitriding. The steel product after nitriding for between 30 and 90 minutes, has a yield strength between 600 MPa and 800 MPa and a tensile strength between 650 MPa and 900 MPa , and has no more than a 2% decrease in total elongation from the steel product prior to nitriding.

Alternatively or additionally, the niobium content may be less than 0.1% by weight. The nitrogen content may be between 0.035 and 0.065% by weight or alternatively may be between 0.045 and 0.065% by weight.

The nitrided steel product may have a yield strength on at least 40% greater than a similar steel composition without nitriding. Alternatively or additionally, the nitrided steel product may have a tensile strength of at least 30% greater than a similar steel composition without nitriding. The yield strength may be between 650 MPa and 800 MPa or may further be between 650 MPa and 750 MPa, and the tensile strength may be between 750 MPa and 900 MPa or may further be between 750 MPa and 850 MPa. The nitrided steel product may have a total elongation of less than 25%, and additionally, the total elongation may be at least 1%, or alternatively, at least 6% or at least 10%.

In addition, a nitrided thin cast steel strip of less than 3 millimeters in thickness comprises, by weight, less than 0.25% carbon, between 0.20 and 2.0% manganese, between 0.05 and 0.50% silicon, less than 0.01% aluminum, niobium between 0.01 and about 0.20%, and between 0.01 and 0.075% nitrogen. The nitrided thin cast steel strip has a majority of the microstructure comprised of bainite and acicular ferrite, with more than 70% niobium in solid solution prior to nitriding. The steel product after nitriding for between 30 and 90 minutes, has a yield strength between 600 MPa and 800 MPa and a tensile strength between 650 MPa and 900 MPa, and has no more than a 2% decrease in total elongation from the steel product prior to nitriding.

Alternatively or additionally, the niobium content may be less than 0.1% by weight. The nitrogen content may be between 0.035 and 0.065% by weight or alternatively may be between 0.045 and 0.065% by weight.

The nitrided thin cast steel strip may have a yield strength on at least 40% greater than a similar steel composition without nitriding. Alternatively or additionally, the nitrided thin cast steel strip may have a tensile strength of at least 30% greater than a similar steel composition without nitriding. The yield strength may be between 650 MPa and 800 MPa or may further be between 650 MPa and 750 MPa, and the tensile strength may be between 750 MPa and 900 MPa or may further be between 750 MPa and 850 MPa.

The nitrided thin cast steel strip may have a total elongation of less than 25%, and additionally, the total elongation may be at least 1%, or alternatively, at least 6% or at least 10%. Further, the thin cast steel strip may have a thickness in the range from about 0.5 mm to about 2 mm.

The nitrided thin cast steel strip may in addition comprise fine oxide particles of silicon and iron distributed through the steel microstructure having an average particle size less than 50 nanometers.

Additionally, a nitrided hot rolled steel product of less than 3 millimeters thickness comprises, by weight, less than 0.25% carbon, between 0.20 and 2.0% manganese, between 0.05 and 0.50% silicon, less than 0.01% aluminum, niobium between 0.01% and 0.20%, and between 0.01 and 0.075% nitrogen, and having a majority of the microstructure comprised of bainite and acicular ferrite and has after nitriding for between 30 and 90 minutes a yield strength between 600 MPa and 800 MPa and tensile strength between 650 MPa and 900 MPa, and no more than a 2% decrease in total elongation from the steel product prior to nitriding.

Alternatively or additionally, the niobium content may be less than 0.1% by weight. The nitrogen content may be between 0.035 and 0.065% by weight or alternatively may be between 0.045 and 0.065% by weight.

The nitrided hot rolled steel product may have a yield strength on at least 40% greater than a similar steel composition without nitriding. Alternatively or additionally, the nitrided hot rolled steel product may have a tensile strength of at least 30% greater than a similar steel composition without nitriding. The yield strength may be between 650 MPa and 800 MPa or may further be between 650 MPa and 750 MPa, and the tensile strength may be between 750 MPa and 900 MPa or may further be between 750 MPa and 850 MPa.

The nitrided hot rolled steel product may have a total elongation of less than 25%, and additionally, the total elongation may be at least 1%, or alternatively, at least 6% or at least 10%. Further, the nitrided hot rolled steel product may have a thickness in the range from about 0.5 mm to about 2 mm.

The nitrided hot rolled steel product may in addition comprise fine oxide particles of silicon and iron distributed through the steel microstructure having an average particle size less than 50 nanometers.

Additionally, a nitrided cold rolled steel product of less than 3 millimeters thickness comprises, by weight, less than 0.25% carbon, between 0.20 and 2.0% manganese, between 0.05 and 0.50% silicon, less than 0.01% aluminum, niobium between 0.01% and 0.20%, and between 0.01 and 0.075% nitrogen, and having a majority of the microstructure comprised of bainite and acicular ferrite and has after nitriding for between 30 and 90 minutes, a yield strength between 600 MPa and 800 MPa and tensile strength between 650 MPa and 900 MPa, and no more than a 2% decrease in total elongation from the steel product prior to nitriding.

Alternatively or additionally, the niobium content of the cold rolled steel product may be less than 0.1% by weight. The nitrogen content may be between 0.035 and 0.065% by weight or alternatively may be between 0.045 and 0.065% by weight.

The nitrided cold rolled steel product may have a yield strength on at least 40% greater than a similar steel composition without nitriding. Alternatively or additionally, the nitrided cold rolled steel product may have a tensile strength of at least 30% greater than a similar steel composition without nitriding. The yield strength may be between 650 MPa and 800 MPa or may further be between 650 MPa and 750 MPa, and the tensile strength may be between 750 MPa and 900 MPa or may further be between 750 MPa and 850 MPa.

The nitrided cold rolled steel product may have a total elongation of less than 25%, and additionally, the total elongation may be at least 1%, or alternatively, at least 6% or at least 10%. Further, the nitrided cold rolled steel product may have a thickness in the range from about 0.5 mm to about 2 mm.

The nitrided cold rolled steel product may in addition comprise fine oxide particles of silicon and iron distributed through the steel microstructure having an average particle size less than 50 nanometers.

Also disclosed is a nitrided age hardened steel product comprising, by weight, less than 0.25% carbon, between 0.20 and 2.0% manganese, between 0.05 and 0.50% silicon, less than 0.01% aluminum, between 0.01% and 0.20% niobium and between 0.01 and 0.075% nitrogen, having a majority of the microstructure comprised of bainite and acicular ferrite and has after nitriding for between 30 and 90 minutes, a yield strength between 600 MPa and 800 MPa and tensile strength between 650 MPa and 900 MPa, and no more than a 2% decrease in total elongation from the steel product prior to nitriding.

Alternatively or additionally, the niobium content of the nitrided age hardened steel product may be less than 0.1% by weight. The nitrogen content may be between 0.035 and 0.065% by weight or alternatively may be between 0.045 and 0.065% by weight.

The nitrided age hardened steel product may have a yield strength on at least 40% greater than a similar steel composition without nitriding. Alternatively or additionally, the nitrided age hardened steel product may have a tensile strength of at least 30% greater than a similar steel composition without nitriding. The yield strength may be between 650 MPa and 800 MPa or may further be between 650 MPa and 750 MPa, and the tensile strength may be between 750 MPa and 900 MPa or may further be between 750 MPa and 850 MPa.

The nitrided age hardened steel product may have a total elongation of less than 25%, and additionally, the total elongation may be at least 1%, or alternatively, at least 6% or at least 10%. Further, the nitrided age hardened steel product may have a thickness in the range from about 0.5 mm to about 2 mm.

The nitrided age hardened steel product may in addition comprise fine oxide particles of silicon and iron distributed through the steel microstructure having an average particle size less than 50 nanometers.

In addition, a method is disclosed for preparing nitrided thin cast steel strip comprising the steps of:

assembling internally a cooled roll caster having laterally positioned casting rolls forming a nip between them, and forming a casting pool of molten steel supported on the casting rolls above the nip and confined adjacent the ends of the casting rolls by side dams,

counter rotating the casting rolls to solidify metal shells on the casting rolls as the casting rolls move through the casting pool,

forming from the metal shells downwardly through the nip between the casting rolls a steel strip, and

cooling the steel strip at a rate of at least 10° C. per second, coiling the cast strip and nitriding the steel strip for between 30 and 90 minutes to provide a composition comprising by weight, less than 0.25% carbon, between 0.20 and 2.0% manganese, between 0.05 and 0.50% silicon, less than 0.01% aluminum, between 0.01% and 0.20% niobium, and between 0.01 and 0.075% nitrogen, and having a majority of the microstructure comprised of bainite and acicular ferrite, having more than 70% niobium in solid solution prior to nitriding and has after nitriding for between 30 minutes and 90 minutes, a yield strength between 600 MPa and 800 MPa and tensile strength between 650 MPa and 900 MPa and no more than a 2% decrease in total elongation from the steel product prior to nitriding. The nitriding process may be selected from the group consisting of salt bath nitriding, gas nitriding, and plasma nitriding. Alternatively or additionally, other nitriding process known to one of ordinary skill in the art are also contemplated.

The steel strip as coiled may have fine oxide particles of silicon and iron distributed through the steel microstructure having an average precipitate size less than 50 nanometers.

The method of preparing nitrided thin cast steel strip may further comprise the steps of:

hot rolling the steel strip; and

coiling the hot rolled steel strip at a temperature between about 450 and 700° C.

Alternatively or additionally, the hot rolled steel strip may be coiled at a temperature less than 650° C.

Also disclosed is a method of preparing a nitrided thin cast steel strip comprising the steps of:

assembling internally a cooled roll caster having laterally positioned casting rolls forming a nip between them, and forming a casting pool of molten steel supported on the casting rolls above the nip and confined adjacent the ends of the casting rolls by side dams,

counter rotating the casting rolls to solidify metal shells on the casting rolls as the casting rolls move through the casting pool, and

forming steel strip from the metal shells cast downwardly through the nip between the casting rolls,

cooling the steel strip at a rate of at least 10° C. per second coiling the cast strip and nitriding the steel strip for between 30 and 90 minutes to provide a composition comprising by weight, less than 0.25% carbon, between 0.20 and 2.0% manganese, between 0.05 and 0.50% silicon, less than 0.01% aluminum, between 0.01% and 0.20% niobium, and between 0.01 and 0.075% nitrogen, and having a majority of the microstructure comprised of bainite and acicular ferrite, having more than 70% niobium in solid solution prior to nitriding and having after nitriding for between 30 and 90 minutes, a yield strength between 600 MPa and 800 MPa and tensile strength between 650 MPa and 900 MPa and no more than a 2% decrease in total elongation from the steel product prior to nitriding, and

age hardening the steel strip before or after nitriding at a temperature between 625° C. and 800° C. The nitriding process may be selected from the group consisting of salt bath nitriding, gas nitriding, and plasma nitriding.

The steel strip as coiled may have fine oxide particles of silicon and iron distributed through the steel microstructure having an average precipitate size less than 50 nanometers.

The age hardened steel strip may have niobium carbonitride particles with an average particle size of 10 nanometers or less. Alternatively or additionally, the age hardened steel strip may have substantially no niobium carbonitride particles greater than 50 nanometers.

The method of preparing nitrided thin cast steel strip may further comprise the steps of:

hot rolling the steel strip; and

coiling the hot rolled steel strip at a temperature less than 700° C.

Alternatively or additionally, the hot rolled steel strip may be coiled at a temperature less than 650° C.

Additionally, the step of age hardening occurs at a temperature between 650° C. and 750° C.

Additionally, a nitrided steel product comprises, by weight, less than 0.25% carbon, between 0.20 and 2.0% manganese, between 0.05 and 0.50% silicon, less than 0.01% aluminum, niobium between 0.01 and about 0.20%, and between 0.01 and 0.075% nitrogen, and has a majority of the microstructure comprised of bainite and acicular ferrite, has more than 70% niobium in solid solution prior to nitriding and has after nitriding for between 30 and 90 minutes an average Vickers hardness at the surface of the steel product at least 50% greater than an average Vickers hardness at the surface of the steel product prior to nitriding.

Additionally, a nitrided steel strip of less than 5 mm in thickness comprises, by weight, less than 0.25% carbon, between 0.20 and 2.0% manganese, between 0.05 and 0.50% silicon, less than 0.01% aluminum, niobium between 0.01 and about 0.20%, and between 0.01 and 0.075% nitrogen, and has a majority of the microstructure comprised of bainite and acicular ferrite, has more than 70% niobium in solid solution prior to nitriding and has after nitriding for between 30 and 90 minutes a soft center portion of less than 250 Vickers hardness and a hard outer portion of greater than 250 Vickers hardness with the hard outer portion being at least 30% of the thickness of the strip.

Additionally, a nitrided steel strip of less than 2 mm in thickness comprises, by weight, less than 0.25% carbon, between 0.20 and 2.0% manganese, between 0.05 and 0.50% silicon, less than 0.01% aluminum, niobium between 0.01 and about 0.20%, and between 0.01 and 0.075% nitrogen, and has a majority of the microstructure comprised of bainite and acicular ferrite, has more than 70% niobium in solid solution prior to nitriding and has after nitriding for between 30 and 90 minutes a soft center portion of less than 250 Vickers hardness and hard outer portion of greater than 250 Vickers hardness with the hard outer portion being at least 30% of the thickness of the strip.

A nitrided steel product comprises, by weight, less than 0.25% carbon, between 0.20 and 2.0% manganese, between 0.05 and 0.50% silicon, less than 0.01% aluminum, niobium between 0.01 and about 0.20%, and between 0.01 and 0.075% nitrogen, and has a majority of the microstructure comprised of bainite and acicular ferrite, has more than 70% niobium in solid solution prior to nitriding and has after nitriding for between 30 and 90 minutes a nitride cluster density of 2600×10¹⁵ clusters/cm³ at a depth of 25 microns below the steel product surface. The nitride clusters may include at least one of the nitrides selected from the consisting of niobium nitride, manganese nitride, chromium nitride, iron nitride, and combinations thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

In order that the invention may be described in more detail, some illustrative examples will be given with reference to the accompanying drawings in which:

FIG. 1 illustrates a strip casting installation incorporating an in-line hot rolling mill and coiler;

FIG. 2 illustrates details of the twin roll strip caster;

FIG. 3 illustrates the effect of nitriding time on strip hardness with and without microalloy additions;

FIG. 4 illustrates the hardness profile on nitrided microalloy steel, heat treated microalloy steel, and the same microalloy steel in the as-received condition

FIG. 5 a is an optical micrograph of a microalloyed steel strip nitrided for four hours;

FIG. 5 b is an optical micrograph of a microalloyed steel strip nitrided for six hours;

FIGS. 6 a-c illustrate atom probe data showing the dispersion of precipitates in specimens as received, after four hour nitriding treatment, and after six hour nitriding treatment, respectively;

FIG. 7 is a graph depicting hardness profiles of niobium microalloyed steel strip in the as-received, one hour nitrided, and two hour nitrided conditions;

FIG. 8 is a stress-strain diagram of niobium microalloyed steel strip in the as-received, one hour nitrided, and two hour nitrided conditions;

FIG. 9 a is an SEM image of the fracture surface of the niobium microalloyed steel strip after nitriding for one hour;

FIG. 9 b is an SEM image of the fracture surface of the niobium microalloyed steel strip after nitriding for two hours;

FIG. 10 is a three dimensional atom map displaying clustering of Nb/NbN, Mn, Cr, and FeN in the nitrided steel strip specimen prepared 25 μm below the surface of the strip after applying the core-linkage algorithm;

FIG. 11 a is a three dimensional atom map displaying clustering of Nb/NbN in the nitrided steel strip specimen prepared 100 μm below the surface of the strip after applying the core-linkage algorithm;

FIG. 11 b is a three dimensional atom map displaying clustering of Nb/NbN in the nitrided steel strip specimen prepared 200 μm below the surface of the strip after applying the core-linkage algorithm;

FIG. 11 c is a three dimensional atom map displaying clustering of Nb/NbN in the nitrided steel strip specimen prepared 500 μm below the surface of the strip after applying the core-linkage algorithm; and

FIG. 12 is a chart showing the number density of atom clusters versus cluster size (in atoms) for specimens taken at depths 25, 100, 200, and 500 μm below the surface of the niobium microalloyed steel following one hour of nitriding at 525° C.

DETAILED DESCRIPTION OF THE DRAWINGS

The following description of the embodiments is in the context of high strength thin cast strip with microalloy additions made by continuous casting steel strip using a twin roll caster. The embodiments described herein are not limited to the use of twin roll casters and extends to other types of continuous strip casters.

FIG. 1 illustrates successive parts of strip caster for continuously casting steel strip. FIGS. 1 and 2 illustrate a twin roll caster 11 that continuously produces a cast steel strip 12, which passes in a transit path 10 across a guide table 13 to a pinch roll stand 14 having pinch rolls 14A. Immediately after exiting the pinch roll stand 14, the strip passes into a hot rolling mill 16 having a pair of reduction rolls 16A and backing rolls 16B where the cast strip is hot rolled to reduce a desired thickness. The hot rolled strip passes onto a run-out table 17 where the strip may be cooled by convection and contact with water supplied via water jets 18 (or other suitable means) and by radiation. The rolled and cooled strip is then passes through a pinch roll stand 20 comprising a pair of pinch rolls 20A and then to a coiler 19. Final cooling of the cast strip takes place after coiling.

As shown in FIG. 2, twin roll caster 11 comprises a main machine frame 21 which supports a pair of laterally positioned casting rolls 22 having casting surfaces 22A. Molten metal is supplied during a casting operation from a ladle (not shown) to a tundish 23, through a refractory shroud 24 to a distributor or movable tundish 25, and then from the tundish 25 through a metal delivery nozzle 26 between the casting rolls 22 above the nip 27. The molten metal delivered between the casting rolls 22 forms a casting pool 30 above the nip. The casting pool 30 is restrained at the ends of the casting rolls by a pair of side closure dams or plates 28, which are pushed against the ends of the casting rolls by a pair of thrusters (not shown) including hydraulic cylinder units (not shown) connected to the side plate holders. The upper surface of casting pool 30 (generally referred to as the “meniscus” level) usually rises above the lower end of the delivery nozzle so that the lower end of the delivery nozzle is immersed within the casting pool 30. Casting rolls 22 are internally water cooled so that shells solidify on the moving roller surfaces as they pass through the casting pool, and are brought together at the nip 27 between them to produce the cast strip 12, which is delivered downwardly from the nip between the casting rolls.

The twin roll caster may be of the kind which is illustrated and described in some detail in U.S. Pat. Nos. 5,184,668 and 5,277,243 or U.S. Pat. No. 5,488,988. Reference may be made to those patents for appropriate construction details of a twin roll caster appropriate for use in an embodiment of the present invention.

A high strength thin cast strip product can be produced using the twin roll caster that overcomes the shortcomings of conventional light gauge steel products and produces a high strength, light gauge, low carbon, steel strip product. Low carbon steel here refers to steels having a carbon level below 0.1% by weight. The invention may utilize microalloying elements including niobium, vanadium, titanium or molybdenum or a combination thereof.

Microalloying elements in steel are commonly taken to refer to the elements titanium, niobium, and vanadium. These microalloying elements were usually added in the past in levels below 0.1%, but in some cases levels as high as 0.2%. These microalloying elements are capable of exerting strong effects on the steel microstructure and properties via a combination of hardenability, grain refining and precipitation strengthening effects (in the past as carbonitride formers). Molybdenum has not normally regarded as a microalloying element since on its own it is a relatively weak carbonitride former, but in the present circumstances carbonitride formation is inhibited in the hot rolled strip with these microalloys as explained below.

The high strength thin cast strip product combines several attributes to achieve a high strength light gauge cast strip product by microalloying with these elements. Strip thicknesses may be less than 5 mm, 3 mm, less than 2.5 mm, or less than 2.0 mm, and may be in a range of 0.5 mm to 2.0 mm. The cast strip is produced by hot rolling without the need for cold rolling to further reduce the strip to the desired thickness. Thus, the high strength thin cast strip product overlaps both the light gauge hot rolled thickness ranges and the cold rolled thickness ranges desired. The strip may be cooled at a rate of 10° C. per second and above, and still form a microstructure that is a majority and typically predominantly bainite.

The benefits achieved through the preparation of such a high strength thin cast strip product are in contrast to the production of previous conventionally produced microalloyed steels which results in relatively high alloy costs, difficulties in hot and cold rolling, and difficulties in recrystallization annealing since conventional continuous galvanizing and annealing lines are not capable of providing the high annealing temperatures needed. Moreover, the relatively poor ductility exhibited with strip made by the cold rolled and recovery annealed manufacturing route is overcome.

The high strength thin cast steel strip product was produced comprising, by weight, less than 0.25% carbon, between 0.20 and 2.00% manganese, between 0.05 and 0.50% silicon, less than 0.01% aluminum, niobium between about 0.01%, and between about 0.01 and 0.075% nitrogen, and having a microstructure comprising a majority bainite and acicular ferrite, having more than 70% niobium in solid solution prior to nitriding. The steel product may further comprising fine oxide particles of silicon and iron distributed through the steel microstructure having an average precipitate size less than 50 nanometers. The steel product may be further comprised of a more uniform distribution of microalloys through the microstructure than previously produced with conventional slab cast product.

After hot rolling, the hot rolled low carbon steel strip may be coiled at a temperature in the range from about 500-700° C. The thin cast steel strip may also be further processed by precipitation hardening the low carbon steel strip to increase the tensile strength at a temperature of at least 550° C. The precipitation hardening may occur at a temperature between 550° C. and 800° C. or more particularly between 675° C. and 750° C. Conventional furnaces of continuous galvanizing or annealing lines are thus capable of providing the precipitation hardening temperatures needed to harden the microalloyed cast strip product.

For example, a steel composition was prepared by making a steel composition of a 0.026% niobium, 0.04% by weight carbon, 0.85% by weight manganese, 0.25% by weight silicon that has been cast by a thin cast strip process. The strip was cast at 1.7 mm thick and inline hot rolled to a range of strip thickness from 1.5 mm to 1.1 mm using a twin roll caster as illustrated in FIGS. 1 and 2. The strip was coiled at coiling temperatures of 590-620° C. (1094-1148° F.).

After coiling, the strip may be subjected to a nitriding processes described herein. Alternatively parts may be formed from the strip by stamping or other processes and then nitrided. In one example, nitriding was performed on a 0.084 wt % Nb-microalloyed steel compositions (Nb-steel) made by twin roll casting with the processing parameters and chemical composition (wt. %) which are listed in Table 1. Steel coupons were heated in a KNO₃ salt bath at 525° C., followed by water quenching. Such a temperature for the salt bath is typical of nitriding salt baths, which generally employ molten salt or salts between about 500° C. and 600° C. LECO combustion analysis was undertaken to determine the N concentration in all samples. For comparison, Nb-free steel compositions made by twin roll casting were also nitrided, and a nitrogen-free heat treatment (achieved by wrapping steel coupons in Al foil) was also carried out on the Nb-steel. Potassium nitrate (KNO₃) starts to decompose at about 500° C. into K₂O, O₂ and N₂, where the N₂ is available to diffuse into steel. Higher temperature nitriding at 650° C. is believed to encourage Fe nitride precipitation mainly at grain boundaries and partly within grains.

TABLE 1 HR Coil Specimen temp(° C.) temp(° C.) Nb C Mn Si N Nb-free steel 878.5 544 0.001 0.034 0.98 0.2 0.008 Nb-steel 897 567 0.084 0.031 0.83 0.2 0.006

Alternatively, other nitriding processes known to one of ordinary skill in the steelmaking arts may also be employed within the scope of the disclosure. For example, the strip may be gas nitrided in a furnace at temperatures between about 500° C. and 575° C., where the furnace atmosphere is rich in nitrogen. Typically, such an atmosphere may include ammonia. During the gas nitriding process, the ammonia gas contacts the heated workpiece and dissociates into nitrogen and hydrogen, with the nitrogen diffusing through the surface of the workpiece and into the body of the workpiece. The rate of introduction of nitrogen to the surface of the workpiece is determined by the nitriding potential, which is determined by the concentration of ammonia at the work surface and the rate of ammonia dissociation. As such, computer systems may be used to control the concentration of ammonia in the furnace in order to effect consistent nitriding treatment.

In another alternative, the strip may be treated by plasma nitriding, which is also known as ion nitriding, plasma ion nitriding, and glow-discharge nitriding. In the plasma nitriding process, the workpiece to be treated is placed in a controlled atmosphere, which typically is nitrogen gas, but additionally may include argon and/or hydrogen. Electrical fields are then used to ionize the nitrogen gas, forming a plasma. The plasma impinges on the surface of the workpiece, effectively nitriding the workpiece. The efficiency of the plasma nitriding process is not temperature dependent, and accordingly, plasma nitriding may be conducted over a broader range of temperatures than either salt bath or gas nitriding, from about 250° C. to temperatures in excess of 600° C.

The nitrogen pick-up measured after nitriding is shown in Table 2. Nitrogen in the samples nitrided for 4 and 6 hours are 7.4 and 9.3 times higher than the as-received sample. Also shown in Table 2 are tensile data from the nitrided steels. There is a small drop of total elongation from 14% to 12% after 4 hours. The fracture type still remains ductile. The YS and UTS of the 4 hour nitrided Nb-steel are 52% and 43% higher than those of the as-received steel. Further nitriding (6 hours) causes a dramatic drop in ductility that leads to brittle fracture. The yield strength (YS), ultimate tensile strength (UTS) and total elongation (TE) for each specimen were obtained using standard tensile testing.

TABLE 2 Nitriding N YS UTS time (h) (wt %) (MPa) (MPa) TE (%) 0 0.006 475.9 ± 1.7 557.1 ± 4.7 14.2 ± 2.3 1 0.025 600.0 ± 2.3 673.0 ± 2.6 11.7 ± 0.2 4 0.059 722.0 ± 1.4 797.5 ± 4.9 12.5 ± 0.5 6 0.072 764 822 5

Referring now to FIG. 3, the hardness profiles show increased hardening for Nb-steel as the duration of nitriding increases. To a lesser extent, surface hardening was also observed with increased nitriding time in the Nb-free steel. Hardness was measured using a Vickers micro-hardness indenter with a load of 5 kg for the surface measurements and 1 kg for the through thickness measurements.

FIG. 4 shows hardness profiles of 4 hour-nitrided Nb-steel, 4 hour-heat-treated Nb-steel without nitrogen diffusion and the same Nb-steel as received in the thickness direction. The hardness of the as-received and the nitrogen diffusion-free samples are uniform across the thickness, while the heat-treated sample is harder. The nitrided Nb-steel is harder towards the surfaces and softer near the center, and the hardness near the center is only slightly higher than that of nitrogen-diffusion-free aged steel.

Turning now to FIGS. 5 a-b, transmission electron microscopy (TEM) studies were carried out using a JEOL 2100 at 200 kV. All TEM specimens were prepared from the center of the steel sheets in the thickness direction. FIG. 5 a shows precipitates in the Nb-steel nitrided for 4 hours, while FIG. 5 b shows coarse grain boundary precipitates in the Nb-steel nitrided for 6 hours. TEM observations revealed a very fine, speckled contrast after nitriding for 4 to 6 hours, indicating a dispersion of very fine precipitates in the 4 hour sample. Additionally, the specimens nitrided for 6 hours also contained coarse features along grain boundaries. These features were occasionally found in the 4 hour nitrided steel but less frequently than in the 6 hour nitrided specimens. No such features were noticed in the as-received steels.

Atom probe tomography (APT) work was performed with a Local Electrode Atom Probe (LEAP) at ˜25 K with a pulse fraction of 25%, a flight path of 90 mm and a pulse repetition rate of 200 kHz. APT data were reconstructed using the method described in B. Gault, M. P. Moody, F. de Geuser, G. Tsafnat, A. La Fontaine, L. T. Stephenson, D. Haley, S. P. Ringer, Journal of Applied Physics 105 (2009). All APT specimens were prepared from the center of the steel sheets in the thickness direction. Similar to the results found by TEM analysis, atom probe tomography also showed a dispersion of fine precipitates in the specimens nitrided for 4 hours and 6 hours, as shown in FIGS. 6 b and 6 c, respectively. Precipitates were observed along dislocations as well as in the matrix. No Nb-rich precipitates were found in atom probe data from the as-received steel, as shown in FIG. 6 a. There were also noticeable (NbN)³⁺ and (NbN)²⁺ clusters present in 4 and 6 hour-nitrided Nb-steels.

Further investigation has found that the overall yield strength of a 0.084 wt % Nb-microalloyed steel, having processing parameters and chemical composition (wt %) as listed in Table 1, may be improved with nitriding from 475 MPa to 640 MPa (corresponding to a 35% change), with no significant change in the total elongation, following one hour of nitriding at 525° C. in a KNO₃ salt bath. In other words, there is not a substantial decrease in total elongation following a nitriding treatment, which may be between 30 and 90 minutes, or more specifically, may be one hour. More specifically, there is no more than a 2% decrease in total elongation from the steel product prior to nitriding when compared to the steel product after nitriding. Such a nitrided steel strip may be formed having a hard-shell-soft-core structure which results in the combined high yield strength and improved ductility relative to the same steel composition without nitriding treatment. The improved strength may be attributed to the N diffusion layers adjacent the surfaces on both sides of the steel sheet providing a hard shell, while the retained ductility is considered to be from the lower-N soft core.

Table 3 summarizes the mechanical properties of some commonly used HSLA steels together with those obtained in this study for the 08Nb steels before and after nitriding for comparison. The yield strength for HSLA steels generally ranges from 300 to 550 MPa with total elongation from 15 to 20%. The 1 hour-nitrided steel strip exhibited very high yield strengths of 645 MPa compared to other conventional HSLA steels, with good ductility of 16%.

TABLE 3 Steel Grade YS (MPa) Ductility (%) A440 290 23 A633 Grade E 380 21 A656 Grade 1 552 15 08 Nb Steel (as-received) 475 16 08 Nb Steel (nitrided 1 hour) 645 16

In one example, hot-rolled 0.084 wt % Nb-microalloyed steel coupons were manufactured via the CASTRIP® process, with bainite and acicular ferrite forming the majority of the microstructure. Steel specimens were then heated in a KNO₃ salt bath at 525° C. to induce nitriding, followed by water quenching. No apparent recrystallization or grain growth was observed from optical micrographs in this study. The yield strength and total elongation for each specimen were obtained using standard tensile tests on dog-bone shaped coupons with a gauge length of 50 mm and a strain rate of 0.008 s⁻¹. Nitrogen pick-up during nitriding for different times were measured by LECO combustion analysis, and hardness values through cross-sections of the samples were measured using a Vickers hardness indenter with a 1 kg load.

FIG. 7 shows the hardness profiles of the as-received, one hour and two hour nitrided steel specimens through the thickness of the steel strip, i.e., from the top of the strip to the bottom of the strip. The hardness of the as-received steel strip was substantially uniform across the thickness, while the nitrided steel specimens displayed relatively higher hardness values near the surfaces of the strip and relatively lower hardness near the center portion of the strip. In other words, there is a gradient in the hardness profile from surface to center and back to surface of the strip, and no sharp single interface was observed to divide the soft core portion and hard shell adjacent the surfaces of the strip. We have found that by nitriding Nb microalloyed steel product, the strong but brittle diffusion layer is adhered on the soft non-diffused core, with a hardness transition between them. This gradient architecture avoids a sharp interface and effectively suppresses the strain localization, offering a uniform plastic deformation while maintaining ductility.

We have found that after one hour of nitriding, an average Vickers hardness at the surface of the steel product is at least 50% greater than an average Vickers hardness at the surface of the steel product prior to nitriding. Alternatively or additionally, we have also found that after one hour of nitriding, the steel strip contains a relatively softer center portion of less than 250 Vickers hardness and a relatively hard outer portion, or shell, of the strip of greater than 250 Vickers hardness. Following one hour of nitriding, the nitrogen content in the steel strip was 0.025 wt %, with an estimated diffusion depth of 240 μm in a 1200 μm thick strip. In such cases, the hard outer portion or shell of the steel strip is at least 30% of the thickness of the strip, with the relatively softer core accounting for about 70% of the thickness of the strip. More specifically, the strip may be at least 40% hard shell and 60% relatively soft core.

Further nitriding up to 2 hours resulted in brittle fracture. It is known that prolonged nitriding results in the formation of coarse iron nitride precipitates, both within grains and along grain boundaries, which may lead to a brittle fracture in the strip. Furthermore, as the nitriding time increased, the core volume fraction reduced. For example, from the hardness profile in FIG. 7, it can be determined that the volume fraction of the soft core of the strip decreased from 60% in 1 hour-nitrided steel to about 42% in the 2 hour-nitrided 08% Nb steel. The decreased proportion of the soft core may not be enough to suppress the strain localization on the hard outer portion, which may also have contributed to the brittle fracture.

FIG. 8 shows stress-strain curves for the 08Nb steel nitrided at 525° C. for one and two hours compared to the as-received steel strip prior to nitriding. The as-received 08% Nb steel has a yield strength of 475 MPa with approximately 16% total elongation. The yield strength increased up to 640 MPa (a corresponding 35% improvement) after one hour KNO₃ salt bath nitriding with no decrease in ductility, i.e, the total elongation is the same in the as-received steel strip as in the same steel strip following one hour of nitriding. Longer nitriding up to two hours further increased the yield strength of the steel strip but resulted in brittle failure during tensile testing. During tensile testing, both the as-received and one hour nitrided steel specimens underwent a substantial amount of plastic deformation before fracture, while the two hour nitrided steel specimens exhibited no appreciable plastic deformation prior to fracture. The increase in yield strength may be attributed to the nitrogen diffusion layer served as hard shell to provide strength while the essentially non-nitrided center region acted as soft core to retain ductility with a gradient hardness profile. The strengthening mechanism in the nitrogen diffusion layer may be a combination of interstitial solid solution strengthening from nitrogen and dispersion strengthening from fine clusters and precipitates. Interstitial elements such as nitrogen and carbon atoms are believed to occupy the voids and interstices among the matrix atoms which may introduce strain fields that hinder the free movement of dislocations, resulting in strengthening.

Fracture surfaces of the steel strip after tensile testing are shown in FIGS. 9 a and 9 b. These images of fracture surfaces from the nitrided steel specimens tests were taken using an FEI Quanta 200 3D scanning electron microscope (SEM). As shown in these FIG. 9 a, the one hour-nitrided steel strip had a highly dimpled fracture surface, characteristic of ductile fracture. In contrast, FIG. 9 b shows cleavage facets on the fracture surface of the two hour-nitrided steel specimens, which is characteristic of a brittle mode of fracture.

Site-specific atom probe tomography (APT) samples were prepared 25, 100, 200 and 500 μm below the surface of the strip by focused ion beam (FIB, FEI-Quanta200 and Zeiss-Auriga). Atom probe samples were prepared at 30 kV and then cleaned using a 5 kV Ga.⁺ beam. The low acceleration voltage in the FIB yields a Ga-free region of interest, resulting in preservation of the original nitride cluster distribution during the FIB process. APT characterization was performed on a Local Electrode Atom Probe (LEAP 3000× Si) operating at ˜40 K with laser energy of 0.3 nJ, a flight path of 90 mm and a pulse repetition rate of 200 kHz, parameters that have previously been found to yield high quality data with a good combination of mass resolution and spatial resolution for this type of steel. APT data were then reconstructed using the protocol described by Gault et al. (Journal of Applied Physics, 105 (2009) 034913-034913-034919) and the parameters used were further confirmed with SEM images post-field evaporation to determine the tip radius. Clusters larger than five atoms were identified and analyzed quantitatively using the core-linkage algorithm reported by Stephenson et al (Microscopy and Microanalysis, 13 (2007) 448-163).

Given the combination of strength and ductility present in the one hour nitrided sample, the microstructure of that steel strip was characterized and investigated using APT. APT results from the strip taken from 25 μm below the surface (the regions directly below the surface to which most strengthening is believed to occur) showed clustering of atoms from the peaks in the mass spectra attributed to Nb/NbN, Mn, Cr and FeN species as shown in FIG. 10. For specimens taken 100, 200 and 500 μm below the strip surface, only clustering from Nb/NbN was observed, and the 3D atom maps from these areas are shown in FIGS. 11 a-11 c, respectively. FIG. 12 summarizes the cluster size versus density distribution. For the specimen taken 25 μm below the surface, clustering species including Nb/NbN, Mn, Cr and FeN were analyzed. Only Nb/NbN species were used in the core-linkage algorithm for the other three specimens (100, 200 and 500 μm below the surface), because no other species other than Nb/NbN were observed to cluster at those sub-surface depths. The measurements taken at 25 μm below the surface of the strip are believed to a higher number density for all sizes of clusters. It may be observed that the cluster density decreased as the specimens were taken further below the strip surface.

Besides the nitrogen interstitial solid solution, a dispersion of nitride clusters is also believed to contribute to the overall strengthening of the nitrided steel strip. The clustering near the surface (where the nitrogen content was high) involved multiple elements and may be attributable to the fact that the alloying elements in the strip cast steel, such as Nb, Mn and Cr, are strong nitride formers. Iron may also form iron nitride in a nitrogen rich environment, such as the nitrided layer of the presently disclosed steep strip. Our experimental observations revealed that Nb, Mn, Cr and FeN species have clustered and co-clustered in the specimen 25 μm below the surface of the strip, as shown in FIG. 10, with a density of 2600×10¹⁵ clusters/cm³.

The clustering in specimens taken from 100, 200 and 500 μm below the surface were observed to mainly contain Nb. Using only the Nb species in these three specimens, the number density of clusters decreases from 630×10¹⁵ to 290×10¹⁵ clusters/cm³ as the measurements gets further away from the surface and closer to the center portion of the strip. As shown in FIG. 12, the measurements closest to the surface of the strip has a significantly larger cluster number density than those taken more towards the center portion, because multiple species such as Nb, Mn, Cr and FeN were selected in the core-linkage analysis. In all specimens, most of the clusters are quite small, consisting of only 10 to 40 atoms (with ˜50% atom probe detection efficiency taken into account), and are therefore extremely difficult to characterize using conventional microscopy techniques.

While the specimen toward the center portion of the steel strip has not been substantially affected by nitrogen diffusion, there are still some Nb-rich clusters present. This may be attributed to the fact that the as received steel contained small amount of N (0.007 wt %) and C (0.03 wt %), so that Nb atoms formed niobium carbonitride clusters upon heating. With use the CASTRIP® process, the thin strip produced may have a retention of at least 70% and possibly approaching 100% of Nb in solution due to the rapid solidification followed by relatively rapid cooling rate of the strip. The relatively high levels of Nb in solution have been found to significantly improve Nb age hardening on reheating. The slightly higher hardness obtained at the center portion of the 1 hour nitrided steel compared to the as-received steel demonstrates the age hardening effect from Nb.

While the invention has been illustrated and described in detail in the foregoing drawings and description, the same is to be considered as illustrative and not restrictive in character, it being understood that only illustrative embodiments thereof have been shown and described, and that all changes and modifications that come within the spirit of the invention described by the following claims are desired to be protected. Additional features of the invention will become apparent to those skilled in the art upon consideration of the description. Modifications may be made without departing from the spirit and scope of the invention. 

1. A nitrided steel product comprising, by weight, less than 0.25% carbon, between 0.20 and 2.0% manganese, between 0.05 and 0.50% silicon, less than 0.01% aluminum, niobium between 0.01 and about 0.20%, and between 0.01 and 0.075% nitrogen, and having a majority of the microstructure comprised of bainite and acicular ferrite, having more than 70% niobium in solid solution prior to nitriding and after nitriding for between 30 and 90 minutes, having yield strength between 600 MPa and 800 MPa and tensile strength between 650 MPa and 900 MPa and no more than a 2% decrease in total elongation from the steel product prior to nitriding.
 2. The nitrided steel product as claimed in claim 1 where the niobium is less than 0.1%.
 3. The nitrided steel product as claimed in claim 1 where the nitrided steel product has yield strength of at least 40% greater than a similar steel composition without nitriding.
 4. The nitrided steel product as claimed in claim 1 where the nitrided steel product has tensile strength of at least 30% greater than a similar steel composition without nitriding.
 5. The nitrided steel product as claimed in claim 1 where the nitrogen is between 0.035 and 0.065%.
 6. The nitrided steel product as claimed in claim 1 where the nitrogen is between 0.045 and 0.065%.
 7. The nitrided steel product as claimed in claim 1 where the nitrided steel product has yield strength between 650 MPa and 750 MPa and tensile strength between 750 MPa and 850 MPa.
 8. The nitrided steel product as claimed in claim 1 where the nitrided steel product has a total elongation of less than 25% than a similar steel composition without nitriding.
 9. The nitrided steel product as claimed in claim 1 where the nitrided steel product has a total elongation of at least 1%.
 10. The nitrided steel product as claimed in claim 1 where the steel product has a total elongation of at least 6%.
 11. The nitrided steel product as claimed in claim 1 where the steel product has a total elongation of at least 10%.
 12. The nitrided steel product as claimed in claim 1 where the steel product is a thin cast steel strip of less than 3 millimeters in thickness.
 13. The nitrided steel product as claimed in claim 12 where the thin cast steel strip is hot rolled.
 14. The nitrided steel product as claimed in claim 12 where the thin cast steel strip is cold rolled.
 15. A method of preparing nitrided thin cast steel strip comprising the steps of: assembling internally a cooled roll caster having laterally positioned casting rolls forming a nip between them, and forming a casting pool of molten steel supported on the casting rolls above the nip and confined adjacent the ends of the casting rolls by side dams, counter rotating the casting rolls to solidify metal shells on the casting rolls as the casting rolls move through the casting pool, and forming from the metal shells downwardly through the nip between the casting rolls a steel strip, and cooling the steel strip at a rate of at least 10° C. per second, coiling the cast strip and nitriding the steel strip for between 30 and 90 minutes to provide a composition comprising by weight, less than 0.25% carbon, between 0.20 and 2.0% manganese, between 0.05 and 0.50% silicon, less than 0.01% aluminum, between 0.01% and 0.20% niobium, and between 0.01 and 0.075% nitrogen, and having a majority of the microstructure comprised of bainite and acicular ferrite, having more than 70% niobium in solid solution prior to nitriding and after nitriding having yield strength between 600 MPa and 800 MPa and tensile strength between 650 MPa and 900 MPa and no more than a 2% decrease in total elongation from the steel product prior to nitriding.
 16. The method of preparing nitrided thin cast steel strip as claimed in claim 15 where the steel strip as coiled may have fine oxide particles of silicon and iron distributed through the steel microstructure having an average particle size less than 50 nanometers.
 17. The method of preparing nitrided thin cast steel strip as claimed in claim 15 further comprising the steps of: hot rolling the steel strip; and coiling the hot rolled steel strip at a temperature between about 450 and 700° C.
 18. The method of preparing nitrided thin cast steel strip as claimed in claim 15 further comprising the steps of: hot rolling the steel strip; and coiling the hot rolled steel strip at a temperature less than 650° C.
 19. The method of preparing a nitrided thin cast steel strip as claimed in claim 15 where the nitriding process is selected from the group consisting of salt bath nitriding, gas nitriding, and plasma nitriding.
 20. A nitrided steel product comprising, by weight, less than 0.25% carbon, between 0.20 and 2.0% manganese, between 0.05 and 0.50% silicon, less than 0.01% aluminum, niobium between 0.01 and about 0.20%, and between 0.01 and 0.075% nitrogen, and having a majority of the microstructure comprised of bainite and acicular ferrite, having more than 70% niobium in solid solution prior to nitriding and having after nitriding for between 30 and 90 minutes, an average Vickers hardness at the surface of the steel product at least 50% greater than an average Vickers hardness at the surface of the steel product prior to nitriding.
 21. A nitrided steel strip of less than 5 mm in thickness comprising, by weight, less than 0.25% carbon, between 0.20 and 2.0% manganese, between 0.05 and 0.50% silicon, less than 0.01% aluminum, niobium between 0.01 and about 0.20%, and between 0.01 and 0.075% nitrogen, and having a majority of the microstructure comprised of bainite and acicular ferrite, having more than 70% niobium in solid solution prior to nitriding and having after nitriding for between 30 and 90 minutes, a soft center portion of less than 250 Vickers hardness and a hard outer portion of greater than 250 Vickers hardness with the hard outer portion being at least 30% of the thickness of the strip.
 22. A nitrided steel strip of less than 2 mm in thickness comprising, by weight, less than 0.25% carbon, between 0.20 and 2.0% manganese, between 0.05 and 0.50% silicon, less than 0.01% aluminum, niobium between 0.01 and about 0.20%, and between 0.01 and 0.075% nitrogen, and having a majority of the microstructure comprised of bainite and acicular ferrite, having more than 70% niobium in solid solution prior to nitriding and having after nitriding for between 30 and 90 minutes, a soft center portion of less than 250 Vickers hardness and hard outer portion of greater than 250 Vickers hardness with the hard outer portion being at least 30% of the thickness of the strip.
 23. A nitrided steel product comprising, by weight, less than 0.25% carbon, between 0.20 and 2.0% manganese, between 0.05 and 0.50% silicon, less than 0.01% aluminum, niobium between 0.01 and about 0.20%, and between 0.01 and 0.075% nitrogen, and having a majority of the microstructure comprised of bainite and acicular ferrite, having more than 70% niobium in solid solution prior to nitriding and having after nitriding for between 30 and 90 minutes, a nitride cluster density of 2600×10¹⁵ clusters/cm³ at a depth of 25 microns below the steel product surface.
 24. The nitrided steel product as claimed in claim 23, where the nitride clusters include at least one of the nitrides selected from the consisting of niobium nitride, manganese nitride, chromium nitride, iron nitride, and combinations thereof. 